CN107429105B

CN107429105B - Coating composition, coating and method for sound and vibration damping and waterproofing

Info

Publication number: CN107429105B
Application number: CN201580073844.1A
Authority: CN
Inventors: 王苇; 赵天杰; D·R·芬; K·T·菲尔普斯
Original assignee: PPG Industries Ohio Inc
Current assignee: PPG Industries Ohio Inc
Priority date: 2014-12-15
Filing date: 2015-12-11
Publication date: 2021-06-15
Anticipated expiration: 2035-12-11
Also published as: KR20170096154A; CA2970943A1; EP3253833A1; US20160168411A1; CN107429105A; RU2676058C1; US9546296B2; CA2970943C; MX2017007782A; ES2881464T3; EP3838997A1; WO2016100130A1; EP3253833B1; MX2023013511A; KR102008075B1

Abstract

Coating compositions are disclosed having a solids content of at least 95% as measured according to test method ASTM D2369. The composition includes a mixture of (a) a polymer prepared from one or more functional monomers, the monomers including a (meth) acrylic monomer, an allyl monomer, or a combination thereof, each having an ethylenically unsaturated double bond and an additional reactive functional group, and (b) a reactive diluent. At least some of the additional reactive functional groups of the functional monomer remain unreacted during the formation of the polymer. The reactive diluent has a boiling point greater than 100 ℃ and a reactive functional group that reacts with the reactive functional group on the polymer at a temperature below the boiling point of the reactive diluent. Also disclosed are substrates having a cured coating thereon formed from the cured coating composition, and methods for providing sound and vibration damping.

Description

Coating composition, coating and method for sound and vibration damping and waterproofing

Technical Field

The present application relates generally to coating compositions and coatings. More particularly, the present application relates to coating compositions exhibiting sound and vibration damping and corresponding coatings obtained therefrom.

Background

Coatings containing volatile components, such as water and/or organic solvents, can experience a reduction in volume as the volatile components evaporate from the surface of the coating. As the volatile component leaves the coating, the shrinking force acts to pull the coating inward in all directions. Without intending to be bound by any particular theory, it is believed that if the coating has sufficient cohesive strength, the coating will shrink only in one degree, in such a way that the thickness of the coating is reduced but the coating resists shrinkage in any direction parallel to the surface of the substrate. Conversely, if the coating lacks sufficient cohesive strength to resist shrinkage parallel to the substrate surface, the shrinking forces will cause the coating to break into small flat pieces separated by gaps or continuous linear voids. Such surface defects are generally referred to as "cracks".

Pre-cut asphalt or rubber based panels may be used to line underbody, trunk lids and doors of automobiles to dampen or reduce road and engine noise and vibration, preventing them from entering the car cabin. Sprayable coatings that can be applied by robots are desirable to provide labor and cost savings, as well as flexibility in design specifications that impart desirable sound and vibration damping properties.

Exposing the coating to water can result in damage to the coating, and absorption of water can increase the coating weight, soften the coating, and/or reduce damping.

Summary of The Invention

According to the invention, the coating composition comprises: a mixture and a filler material, the mixture comprising: (a) a polymer prepared from one or more functional monomers comprising (meth) acrylic monomers, allyl monomers, or combinations thereof, each having an ethylenically unsaturated double bond and an additional reactive functional group, wherein at least some of the additional reactive functional groups of the functional monomers remain unreacted during formation of the polymer; and (b) a reactive diluent having a boiling point greater than 100 ℃ and containing a reactive functional group that reacts with the reactive functional group on the polymer at a temperature below the boiling point of the reactive diluent; wherein the coating composition has a solids content of at least 95% as measured according to test method ASTM D2369.

According to the present invention, the above-described coating composition, when applied to a substrate and cured, has a dry film thickness of at least 1 mm.

According to the invention, a method for providing damping of sound and oscillations through a substrate comprises: applying the coating composition to the substrate; and at least partially curing the coating composition.

Detailed Description

As used herein, plural terms include the singular counterpart thereof, and vice versa, unless explicitly stated otherwise. For example, although reference is made herein to "a" (meth) acrylic monomer, "an" allyl monomer, "a" reactive diluent, "a" polymer, "a" monomer, and "a" filler material, combinations (i.e., multiple) of these components may also be used.

As used herein, terms "comprising," "including," and the like, are to be understood in the context of this application as being synonymous with "comprising" and thus open-ended, and do not preclude the presence of additional unrecited or unrecited elements, materials, ingredients, or method steps. As used herein, "consisting of …" is understood in the context of the present application to exclude the presence of any element, ingredient, or method step not explicitly recited. As used herein, "consisting essentially of …" is understood in the context of this application to include the elements, components, or method steps specifically identified as well as those elements, components, or method steps that do not materially affect the basic and novel characteristics of the subject matter being described.

When a closed or open numerical range is described herein, all numbers, values, amounts, percentages, sub-ranges and fractions within or encompassed by that numerical range are to be considered as specifically included in and falling within the original disclosure of the application as if those numbers, values, amounts, percentages, sub-ranges and fractions were expressly written in their entirety.

As used herein, unless otherwise expressly specified, all numbers such as those expressing values, amounts, percentages, subranges and fractions are read as if prefaced by the word "about", even if the term does not expressly appear.

As used herein, the terms "on …", "onto …", "applied on …", "applied on …", "formed on …", "deposited on …", "deposited on …" refer to being formed, covered, deposited or provided on a surface, but not necessarily in contact with the surface. For example, a coating layer "formed on" a substrate does not preclude the presence of one or more additional coating layers of the same or different composition located between the formed coating layer and the substrate.

The term "reactive diluent" as used herein refers to an organic compound that is capable of chemically reacting (e.g., forming a covalent bond) with a polymer (such as the polymers described herein), another species of reactive diluent, and/or its own species of reactive diluent at a temperature below the boiling point of the reactive diluent. As used herein with respect to a reactive diluent, "another species" refers to an organic compound that has a different chemical structure than the reactive diluent, but is capable of chemically reacting with the reactive diluent and/or the polymer. As used herein with respect to a reactive diluent, the term "its own species" refers to another organic compound having the same chemical structure as the reactive diluent.

As used herein with respect to any monomer, generally refers to a monomer that can be polymerized with another polymerizable component such as another monomer, polymer, or reactive diluent. Unless otherwise specified, it will be appreciated that once a monomer component is reacted with another component to form a compound, the compound will include the residue of such component.

The term "polymer" as used herein refers to prepolymers, oligomers, homopolymers, copolymers, and blends or mixtures thereof.

As used herein, "(meth) acrylate" includes both acrylate and methacrylate monomers.

As used herein, "(meth) acrylic" includes acrylic, methacrylic, and derivatives of any of these.

The term "functional monomer" as used herein refers to a monomer used to prepare the polymer, which has an ethylenically unsaturated double bond and an additional reactive functional group. As used herein, "additional reactive functional groups," when used with respect to a functional monomer or a polymer prepared therefrom, refers to reactive functional groups other than the ethylenically unsaturated double bonds of the functional monomer used to prepare the polymer. For clarity, the additional reactive functional group may be a second ethylenically unsaturated double bond.

The term "acid functional group" as used herein includes any acidic functional group including, for example, carboxylic acid functional groups, as well as salts thereof.

As used herein, unless otherwise specified, the term "substantially free" means that the specified material is not intentionally added to the composition, but is present as a trace amount of impurities of less than 1 wt.%, based on the total weight of the composition. As used herein, unless otherwise specified, the term "completely free" means that the composition does not contain the specified material, i.e., the composition contains 0 wt.% of the material.

As used herein, the term "solvent" includes water, organic solvents, and combinations thereof, wherein the organic solvent does not have a reactive functional group capable of reacting with the reactive functional group of the polymer or the reactive functional group of the reactive diluent under typical curing conditions under which a coating composition is at least partially cured, as described in more detail below.

As noted above, the present disclosure relates to a coating composition comprising: a mixture and a filler material, the mixture comprising: (a) a polymer prepared from one or more functional monomers comprising (meth) acrylic monomers, allyl monomers, or combinations thereof, each having an ethylenically unsaturated double bond and an additional reactive functional group, wherein at least some of the additional reactive functional groups of the functional monomers remain unreacted during formation of the polymer; and (b) a reactive diluent having a boiling point greater than 100 ℃ and containing a reactive functional group that reacts with the reactive functional group on the polymer at a temperature below the boiling point of the reactive diluent; wherein the coating composition has a solids content of at least 95% as measured according to test method ASTM D2369.

According to the invention, the functional monomer has, in addition to the ethylenically unsaturated functional group, at least one further reactive functional group. As discussed above, the additional reactive functional groups remain unreacted during formation of the polymer. Thus, the polymer formed from the functional monomer comprises the additional reactive functional group of the functional monomer. Thus, it will be understood that polymerisation of the functional monomer occurs predominantly through unsaturation, but it is possible that some of the further reactive functional groups also react during polymerisation. The polymer may be a homopolymer prepared from a functional monomer containing a reactive functional group. Alternatively, the polymers of the present invention may be copolymers prepared from different functional monomers containing reactive functional groups. If two or more different functional monomers are used, the reactive functional groups on each may be the same or different.

According to the present invention, the reactive functional group of the functional monomer may include, for example, an epoxy group, a hydroxyl group, an anhydride group, an amino group, an acid functional group (such as a carboxylic acid group or a sulfonic acid group), or a combination thereof.

According to the invention, the polymer may be an epoxy-containing (meth) acrylate or allyl copolymer prepared from an ethylenically unsaturated composition comprising: (i) one or more ethylenically unsaturated monomers having at least one epoxy group, and (ii) one or more ethylenically unsaturated monomers free of epoxy groups, with the proviso that at least one of the ethylenically unsaturated monomers of (i) and/or (ii) is a (meth) acrylic or allyl monomer containing a reactive functional group.

Non-limiting examples of ethylenically unsaturated monomers having at least one epoxy group are those containing a 1, 2-epoxy group and include glycidyl (meth) acrylate, allyl glycidyl ether, or combinations thereof.

Non-limiting examples of ethylenically unsaturated monomers that do not contain epoxy groups are alkyl esters of (meth) acrylic acid containing 1 to 20 atoms in the alkyl group. Suitable alkyl esters of (meth) acrylic acid include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Suitable other copolymerizable ethylenically unsaturated monomers that do not contain epoxy groups include, for example, vinyl aromatic compounds such as styrene and vinyl toluene; nitriles such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride; and vinyl esters such as vinyl acetate.

According to the present invention, the epoxy group containing ethylenically unsaturated monomer may be used in an amount of at least 5 wt%, such as at least 20 wt%, such as at least 40 wt%, such as at least 50 wt%, based on the total weight of the ethylenically unsaturated composition used to prepare the epoxy group containing acrylic polymer. According to the present invention, the epoxy-containing ethylenically unsaturated monomer may be used in an amount of not more than 95 wt%, such as not more than 80 wt%, such as not more than 40 wt%, such as not more than 50 wt%, based on the total weight of the ethylenically unsaturated composition used to prepare the epoxy-containing (meth) acrylate polymer.

According to the present invention, the epoxy group-containing ethylenically unsaturated monomer may be used in an amount of 5 to 50% by weight, such as 20 to 40% by weight, based on the total weight of the ethylenically unsaturated composition used to prepare the epoxy group-containing (meth) acrylic polymer. In the present invention, 40 to 95 weight percent, such as 50 to 80 weight percent, based on the total weight of the ethylenically unsaturated composition, can be comprised of one or more alkyl esters of (meth) acrylic acid.

According to the invention, the functional monomer may have a boiling point of at least 100 ℃, such as at least 115 ℃, such as at least 150 ℃, such as at least 250 ℃.

In preparing the epoxy-containing (meth) acrylate copolymer, (i) one or more ethylenically unsaturated monomers having at least one epoxy group, and (ii) one or more ethylenically unsaturated monomers containing no epoxy group (provided that at least one of the ethylenically unsaturated monomers of (i) and/or (ii) is a (meth) acrylate monomer containing a reactive functional group) may be mixed and reacted by conventional free radical initiated organic solution polymerization in the presence of a suitable catalyst such as an organic peroxide or azo compound, for example, benzoyl peroxide or N, N' -azobis (isobutyronitrile).

The polymerization can be carried out in an organic solution in which the monomers are soluble. Suitable solvents are aromatic solvents, such as xylene and toluene, and ketones, such as methyl amyl ketone. In addition, continuous polymerization techniques may be used, such as described in more detail below with respect to acid functional acrylic polymers. "soluble monomer" in the context of this application refers to a homogeneous mixture of monomers that does not undergo phase separation.

The polymers of the present invention may be substantially free, or in some cases completely free, of acid functional groups, for example, (meth) acrylic acid, maleic acid, fumaric acid, partial esters of maleic acid, partial esters of fumaric acid, partial esters of itaconic acid, and combinations thereof.

The polymer of the present invention can be an epoxy functional acrylic utilizing a relatively small amount of initiator (i.e., less than 10 weight percent, based on total monomer weight) by employing a continuous process at high temperatures (i.e., greater than 200 ℃, such as 210-. For example, the temperature may range from 150 ℃ to 280 ℃, such as 160 ℃ to 230 ℃, or 170 ℃ to 210 ℃. The polymerization may be carried out in the substantial absence of lewis acids and/or transition metals.

Any suitable free radical polymerization initiator may be used in making the epoxy-functional acrylic polymer, such as a thermal free radical initiator. Suitable thermal free radical initiators include, but are not limited to, peroxide compounds, azo compounds, and persulfate compounds. The amount of initiator used may be from 0.01 to 0.5 moles of initiator per mole of ethylenically unsaturated composition.

Continuous processes for polymerization are also described in U.S. Pat. No.7,323,529, column 4, line 56 to column 12, line 65, the cited sections being incorporated herein by reference. Epoxy-functional acrylic polymers can be made by a continuous polymerization process using at least two stirred tank reactors, such as described in U.S. patent No.7,323,529, column 9, lines 22-33. In addition, the contents of the first reactor can be maintained at a temperature substantially higher than the contents of the second reactor (e.g., when the contents of the first reactor are maintained at a temperature greater than 200 deg.C, such as 210-. According to the present invention, greater than 50 weight percent, such as at least 70 weight percent, or in some cases at least 80 weight percent of the total initiator used for the reaction is used in the first reactor. Furthermore, the residence time of the contents of the first reactor may not exceed 20 minutes, such as 1 to 20 minutes or 1 to 10 minutes. According to the invention, the residence time of the contents of the second reactor may exceed 20 minutes, such as over 20 minutes to 1 hour, or 30 minutes to 1 hour. "residence time" is defined in U.S. Pat. No.7,323,529 column 8, lines 54-57.

The polymerization of the present invention may be conducted under conditions such that the reaction product contains residual free monomer in an amount less than 1 weight percent, such as less than 0.5, or in some cases less than 0.25 weight percent, based on the total weight of monomers used to prepare the polymer.

According to the present invention, the polymer may comprise at least 1 wt% of functional monomers comprising an ethylenically unsaturated double bond and further reactive functional groups, based on the total monomer weight, such as at least 5 wt%, or at least 30 wt%. According to the present invention, the polymer may comprise 100 wt.% of the functional monomer, based on the total monomer weight, or may comprise no more than 90 wt.% of the functional monomer, based on the total monomer weight, such as no more than 70 wt.%, or no more than 50 wt.%.

According to the invention, the glass transition temperature (T) of the polymer_g) (° c) can be, for example, -55 ℃ to 150 ℃, e.g., 0 ℃ to 60 ℃, using differential scanningCalorimetry (DSC) such as a Perkin Elmer Series 7 differential scanning calorimeter is performed at a scan rate of 20 deg.C/minute.

According to the invention, the weight-average molecular weight (M) of the polymer_w) Can be at least 1,000g/mol, as determined by gel permeation chromatography using polystyrene standards in Tetrahydrofuran (THF), such as at least 3,000g/mol, such as at least 5,000g/mol, such as at least 9,000g/mol, such as at least 150,000 g/mol.

According to the invention, the weight-average molecular weight (M) of the polymer_w) May be no more than 1,000,000g/mol, as determined by gel permeation chromatography using polystyrene standards in Tetrahydrofuran (THF), such as no more than 100,000g/mol, such as no more than 30,000g/mol, such as no more than 9,000g/mol, such as no more than 5,000g/mol, such as no more than 3,000 g/mol.

Weight average molecular weight (M) of the Polymer of the present invention_w) Can range from 1,000 g/mole to 1,000,000 g/mole as determined by gel permeation chromatography using polystyrene standards in Tetrahydrofuran (THF). The polymers of the present invention may have a weight average molecular weight (M)_w)1,000g/mol to 100,000g/mol, including, for example, 1,000g/mol to 3,000g/mol, 3,000g/mol to 5,000g/mol, 5,000g/mol to 9,000g/mol, and 9,000g/mol to 30,000 g/mol. The polymer may have a weight average molecular weight (M) of at least 150,000g/mol_w)。

According to the present invention, the polymer may further comprise monomers other than (meth) acrylic monomers or allyl monomers having an ethylenically unsaturated double bond and additional reactive functional groups, including, for example, styrene, (meth) acrylate monomers which may be different from the above functional monomers, acrylonitrile monomers, acrylamide monomers, terpene monomers and combinations thereof. Terpenes as used herein include alpha-pinene, beta-pinene, terpinene, limonene (dipentene), beta-terpinene, gamma-terpinene, alpha-thujene, sabinene, delta-3-carene, camphene, beta-cadinene, beta-caryophyllene, cedrene, alpha-bisalbone, beta-bisalbone, gamma-bisalbone, zingiberene, humulene, (alpha-caryophyllene-1-ene), alpha-citronellol, linalool, geraniol, nerol, brevicenol, alpha terpineol, D-terpineol- (4), dihydronerolidol, farnesol, alpha-cineol, beta-cineol, citral, D-citronellal, carvone, D-pulegone, piperitone, carbendazine, bisabolene, beta-santaline, alpha-santaline, vitamin A, pineal acid and mixtures of these compounds.

As mentioned above, the mixture further comprises a reactive diluent having a boiling point of greater than 100 ℃, such as greater than 150 ℃, such as greater than 200 ℃, for example. The reactive diluent of the present invention may have a boiling point of less than 350 ℃, such as less than 300 ℃, such as less than 250 ℃, for example. The reactive diluent of the present invention may contain a reactive functional group that reacts with another reactive functional group remaining in the above-mentioned polymer, another kind of reactive diluent, and/or the own kind of reactive diluent at a temperature lower than the boiling point of the reactive diluent.

According to the invention, the reactive diluent may be monofunctional, difunctional or polyfunctional. According to the present invention, the reactive functional group of the reactive diluent may be, for example, an epoxy functional group, an unsaturated ethylene double bond functional group, a terpene functional group, or a combination thereof.

The reactive diluent of the present invention may include glycidyl esters, e.g., branched C₉-C₁₁Glycidyl esters of carboxylic acids, isomers thereof, and combinations thereof. The glycidyl ester can be a glycidyl ester such as, for example, 2,2,3, 5-tetramethylhexanoic acid, 2, 4-dimethyl-2-isopropylpentanoic acid, 2, 5-dimethyl-2-ethylhexanoic acid, 2, 2-dimethyloctanoic acid, 2, 2-diethylhexanoic acid, and combinations thereof. The reactive diluent may include a glycidyl ester of neodecanoic acid.

According to the present invention, the reactive diluent may have an epoxy equivalent weight according to ASTM 1652 of at least 50g/mol, such as at least 200 g/mol. According to the present invention, the reactive diluent may have an epoxy equivalent weight according to ASTM 1652 of not more than 500g/mol, such as not more than 300g/mol, such as not more than 200 g/mol.

According to the present invention, the reactive diluent may have an epoxy equivalent weight according to ASTM D1652 of from 50g/mol to 500g/mol, including for example from 50g/mol to 200g/mol, and from 200g/mol to 300 g/mol.

The reactive diluent may reduce the viscosity of the mixture. The reactive diluents of the invention may have a viscosity at 25 ℃ according to ASTM D789 of from 1 mPas to 4,000 mPas, such as, for example, from 1 mPas to 3,000 mPas, from 1 mPas to 2,000 mPas, from 1 mPas to 1,000 mPas, from 1 mPas to 100 mPas, or from 2 mPas to 30 mPas.

The reactive diluent of the present invention may be a monomer or a polymer.

As previously mentioned, the coating composition comprises a mixture comprising said polymer and said reactive diluent as described above. The polymer of the invention and the reactive diluent may be present in a single phase to form the mixture. Alternatively, the mixture may be a dispersion, such as a non-aqueous dispersion, in which the polymer is dispersed in the reactive diluent. The polymer may be present in the dispersion as polymer particles, such as polymer microparticles described in more detail below.

The term "non-aqueous" as used herein with respect to non-aqueous dispersions means that the reactive diluent is substantially free, or in some cases completely free, of water. The term "dispersion" as used herein with respect to non-aqueous dispersions refers to a two-phase transparent, translucent, or opaque system wherein the polymer is in the dispersed phase and the reactive diluent is in the continuous phase. As used herein, the term "stable non-aqueous dispersion" is understood to mean that the polymer particles that are at least partially, significantly and/or completely insoluble in the non-aqueous medium (e.g., organic solvent and/or reactive diluent) are capable of being distributed in the non-aqueous medium as finely divided, discrete and individual particles, and do not substantially settle, coagulate and/or flocculate during manufacture or standing.

As used herein, the term "substantially free," when used in reference to a non-aqueous dispersion, means that water is not intentionally added to the non-aqueous dispersion, but is merely a trace amount below 5 wt.% as an impurity, based on the total weight of the non-aqueous dispersion. As used herein, unless otherwise specified, the term "completely free" means that the non-aqueous dispersion does not contain the particular material, i.e., the non-aqueous dispersion contains 0 wt.% of that material (e.g., water).

The polymers of the present invention may be in the form of particle dispersions, non-aqueous dispersions, or microgels, as described in U.S. publication No.20120149820 paragraphs [0004] - [0023], U.S. publication No.20140128508 paragraphs [0006] - [0027], and U.S. publication No.20120282475 paragraphs [0006] - [0021], each of which is incorporated herein by reference. The polymer as a combined composition of the core and the shell and the reactive diluent may be present as a mixture.

According to the invention, the polymer and the reactive diluent may be present in the mixture in an amount totaling at least 20 wt. -%, such as at least 30%, such as at least 40%, such as at least 50%, based on the total weight of the mixture comprising the polymer and the reactive diluent. According to the present invention, the polymer and the reactive diluent may be present in the mixture in an amount which in total does not exceed 100 wt. -%, such as not exceeding 80 wt. -%, such as not exceeding 70 wt. -%, such as not exceeding 40 wt. -%, based on the total weight of the mixture comprising the polymer and the reactive diluent.

According to the present invention, the polymer and the reactive diluent may be present in the mixture in an amount totaling from 20 to 100 wt%, based on the total weight of the mixture comprising the polymer and reactive diluent, such as from 30 to 80 wt%, from 40 to 70 wt%, or from 50 to 60 wt%.

According to the present invention, the polymer may be present in the mixture in an amount of at least 30 wt. -%, such as at least 40 wt. -%, such as at least 50 wt. -%, such as at least 70 wt. -%, based on the total weight of the mixture comprising the polymer and the reactive diluent. According to the present invention, the polymer may be present in the mixture in an amount of not more than 95 wt. -%, such as not more than 80 wt. -%, such as not more than 60 wt. -%, based on the total weight of the mixture comprising the polymer and the reactive diluent.

According to the invention, the polymer may be present in the mixture in an amount of 30 to 95 wt. -%, for example, 40 to 80 wt. -%, such as 50 to 60 wt. -%, such as 70 to 80 wt. -%, based on the total weight of the mixture of the polymer and the reactive diluent.

According to the present invention, the reactive diluent may be present in the mixture in an amount of at least 5 wt.%, such as at least 10 wt.%, such as at least 30 wt.%, based on the total weight of the mixture comprising the polymer and the reactive diluent. According to the present invention, the reactive diluent may be present in the mixture in an amount of no more than 70 wt. -%, such as no more than 50 wt. -%, such as no more than 40 wt. -%, such as no more than 20 wt. -%, based on the total weight of the mixture comprising the polymer and the reactive diluent.

According to the invention, the reactive diluent may be present in the mixture in an amount of from 5 to 70 wt. -%, for example, from 10 to 50 wt. -%, such as from 30 to 40 wt. -%, such as from 10 to 20 wt. -%, based on the total weight of the mixture of polymer and reactive diluent.

According to the invention, the mixture comprising the polymer and the reactive diluent, in the absence of filler or any other component, may have a Brookfield viscosity of from 1,000 centipoise to 25,000 centipoise. Measured at ambient/room temperature (25 ℃) at 100rpm with a #6 spindle, includes, for example, brookfield viscosities of 1,000 cps to 20,000 cps, 2,000 cps to 8,000 cps, 3,000 cps to 6,000 cps, 4,000 cps to 5,000 cps.

According to the present invention, the mixture comprising the polymer and the reactive diluent may further comprise a second polymer prepared from monomers comprising an epoxy-functional acrylate material. The second polymer may be dispersed in the reactive diluent as a partially non-aqueous dispersion.

According to the present invention, the mixture and/or coating composition may further comprise one or more polymeric film-forming materials chemically different from the polymeric particles described above. Non-limiting examples of useful polymeric film-forming materials include polyepoxides, polyurethanes, polyamides, polyesters, polyacrylates, polyvinyl chlorides, and mixtures and copolymers thereof.

Except beforeThe mixture and/or coating composition of the present invention may further comprise polyepoxides having at least two epoxy or oxirane groups per molecule, and include epoxy-functional oligomers, polymers and/or copolymers, such as those prepared from monomers comprising epoxy-functional acrylate materials. In general, the epoxy equivalent weight of such epoxy functional polymers may range from 70 to 4,000 as measured by titration with perchloric acid and quaternary ammonium bromide and using methyl violet as an indicator. Suitable epoxy-functional polymers may be saturated or unsaturated, cyclic or acyclic, aliphatic, cycloaliphatic, aromatic or heterocyclic. The epoxy functional polymer may have pendant or terminal hydroxyl groups as desired. The epoxy-functional polymer may contain one or more functional groups and/or substituents, non-limiting examples of which include halogen atoms, hydroxyl groups, and ether groups. Useful classes of these materials include polyepoxides, including epoxy polyethers, obtained by reacting an epihalohydrin (such as epichlorohydrin or epibromohydrin) with a di-or polyhydric alcohol in the presence of a base such as the diglycidyl ether of bisphenol A, for example

828 epoxy resins, available from Momentive.

Non-limiting examples of useful thermoplastic polymeric film-forming materials include polyvinyl acetate; an aromatic vinyl polymer; vinyl copolymers having a vinyl aromatic hydrocarbon as a monomer component, such as polystyrene, styrene-butadiene copolymers, styrene-divinylbenzene copolymers and styrene-acrylonitrile copolymers; saturated polyesters including saturated aliphatic polyesters such as poly (neopentyl glycol adipate), poly (propylene glycol adipate) and poly (epsilon-caprolactone); polyacrylates such as polyalkyl (meth) acrylates having alkyl groups with 1 to 8 carbon atoms, polymethacrylates, or polyalkyl (meth) acrylates obtained by polymerization of methyl methacrylate isobutyl methacrylate and 2-ethylhexyl acrylate; a saturated polyester polyurethane; polybutadiene; polyvinyl chloride and polyvinyl chloride/acetate. Useful substantially saturated polyesters can be prepared from polyfunctional acids and polyhydric alcohols by a variety of methods, including those disclosed in U.S. patent No.4,739,019, column 3, line 22 to column 5, line 15.

If present, the film-forming material may be incorporated into the mixture and/or coating composition comprising the polymer and the reactive diluent in an amount of 1% to 40% by weight, such as may include, for example, 5% to 30% by weight, based on the total resin solids of the mixture and/or coating composition.

As noted above, the coating composition of the present invention also includes a filler material. The filler material may be selected from an organic filler material, an inorganic filler material, or a combination thereof. The filler material may be capable of improving the sound and vibration damping properties of a coating obtained from an at least partially, significantly and/or fully cured coating composition.

The organic filler material may include various forms of natural and/or synthetic materials (e.g., powders, particles, grains, pellets, flakes, fibers, expandable spheres, foaming agents, etc.). Non-limiting examples of such organic filler materials include various forms of plant materials (e.g., cellulose, lignin, starch, rayon, etc.), animal materials (e.g., chitin, chitosan, etc.), and/or synthetic materials (e.g., waxes, polypropylene, high molecular weight polyethylene, etc.).

Non-limiting examples of inorganic filler materials include mica, powdered slate, montmorillonite flakes, glass flakes, metal flakes, talc, metal oxides, calcium oxide, iron oxide, clay minerals, mineral fibers, glass beads, glass bubbles or hollow spheres, ferrite, calcium silicate, calcium carbonate, barite, silica, aluminum hydroxide, alumina, and mixtures thereof.

The filler material of the present invention may be present in the coating composition in an amount of at least 20 wt.%, such as at least 30 wt.%, such as at least 40 wt.%, based on the total weight of the coating composition. The filler material of the present invention may be present in the coating composition in an amount of no more than 80 wt.%, such as no more than 70 wt.%, such as no more than 60 wt.%, based on the total weight of the coating composition.

According to the present invention, the filler material may be present in the coating composition in an amount of from 20 to 80 wt.%, based on the total weight of the coating composition, for example, from 30 to 70 wt.%, or from 40 to 60 wt.%.

The coating compositions of the present invention can have a measured solids content of at least 95%, based on the total weight of the composition, including, for example, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.5%, at least 99.6%, or at least 99.7%, based on the total weight of the composition, measured according to test method ASTM D2369.

The compositions of the present invention may be substantially free of solvent. Alternatively, the composition may be completely free of solvent. As used herein, the term "substantially free" when used to refer to the absence of solvent in the composition means that any solvent is present in the composition in a trace amount of less than 5% based on the total weight of the composition. The term "completely free" when used to refer to the absence of solvent in the composition means that there is no solvent at all in the composition.

The coating composition of the present invention may further comprise one or more optional ingredients, additives and/or auxiliary agents that may be selected based on the particular application of the coating composition. Non-limiting examples of such optional ingredients, additives and/or auxiliary agents include waxes, plasticizers, surfactants (e.g., migrating surfactants), detergents, thixotropic agents, catalysts, initiators, accelerators, polymeric fibers, polymeric beads, polymeric bubbles or hollow spheres, ground natural or synthetic rubbers, dyes, pigments, organic filler materials, carbon black, graphite, graphene, cellulosic fibers, carbon fibers, calcium carbonate, calcium magnesium carbonate, stabilizers, corrosion inhibitors, blowing agents, antioxidants and non-reactive diluents. The coating composition may further comprise a polymeric chain extender. Alternatively, the coating composition may be substantially free, or in some cases completely free, of polymeric chain extenders.

Suitable thixotropic agents include fumed silica, bentonite, stearic acid coated calcium carbonate, fatty acid derivatives, and associative polyurethane thickeners such as ACRYSOL RM-8, which is commercially available from Rohm and Haas. Thixotropic agents may generally be present in amounts up to 20 percent by weight, based on the total weight of the coating composition.

Non-limiting examples of such catalysts include dicyandiamide, sulfur, and combinations thereof. The catalyst of the present invention is capable of catalyzing a reaction between the polymer and the reactive diluent, a reaction between the reactive functional group of the polymer and the reactive functional group of the reactive diluent at a temperature below the boiling point of the reactive diluent, or a combination thereof.

The coating composition of the present invention may further comprise a plasticizer. A plasticizer may be dispersed in the reactive diluent with the polymer. Non-limiting examples of suitable plasticizers include adipates, benzoates, pentamethyleneisophthalate, phosphates, polyesters, sebacates, sulfonamides, terephthalates, and combinations thereof.

The one or more optional ingredients, additives and/or auxiliary agents may typically be present in the coating composition in an amount of from 0.1 to 50 wt. -%, such as from 0.5 to 40 wt. -%, such as from 1 to 30 wt. -%, such as from 1 to 10 wt. -%, based on the total weight of the coating composition.

Once polymerization is complete, the resulting product of the present invention can be a stable, non-aqueous dispersion of polymer particles that are insoluble in non-aqueous media (e.g., organic solvents and/or reactive diluents). Thus, the non-aqueous medium is substantially free of soluble polymers. As used herein, "substantially free" means that the non-aqueous medium contains no more than 30% by weight of dissolved polymer, including, for example, no more than 25%, no more than 20%, no more than 15%, no more than 10%, or no more than 5% by weight of dissolved polymer.

If not already present, the reactive diluent can be added to the stable non-aqueous dispersion of polymer particles before, during, and/or after removal (e.g., stripping under vacuum) of the non-aqueous medium and replacement by the reactive diluent, thereby producing a stable non-aqueous dispersion comprising polymer particles that are at least partially, significantly, and/or completely insoluble in the non-aqueous medium (e.g., solvent), and that are distributed as finely divided, discrete, and independent particles in the non-aqueous medium and that do not substantially settle, coagulate, and/or flocculate during manufacture or standing.

The viscosity of the coating composition is application-based, for example, based on the type of equipment used, the desired/desired film thickness, and/or the desired/desired sag resistance. For example, the coating composition can have a brookfield viscosity of greater than 10,000 cps, measured at ambient temperature (25 ℃) with a #7 spindle at 4rpm to 100rpm, including, for example, 10,000 cps to 1,000,000 cps, 50,000 cps to 800,000 cps, 100,000 cps to 700,000 cps, or 200,000 cps to 500,000 cps.

According to the present invention, in some cases, the coating composition may include: a mixture and a filler material, the mixture consisting of: (a) a polymer prepared from one or more functional monomers comprising (meth) acrylic monomers, allyl monomers, or combinations thereof, each having an ethylenically unsaturated double bond and an additional reactive functional group, wherein at least some of the additional reactive functional groups of the functional monomers remain unreacted during formation of the polymer; and (b) a reactive diluent having a boiling point greater than 100 ℃ and containing a reactive functional group that reacts with the reactive functional group on the polymer at a temperature below the boiling point of the reactive diluent; wherein the coating composition has a solids content of at least 95% as measured according to test method ASTM D2369.

According to the present invention, in some cases, the coating composition may comprise: a mixture and a filler material, the mixture consisting essentially of: (a) a polymer prepared from one or more functional monomers comprising (meth) acrylic monomers, allyl monomers, or combinations thereof, each having an ethylenically unsaturated double bond and an additional reactive functional group, wherein at least some of the additional reactive functional groups of the functional monomers remain unreacted during formation of the polymer; and (b) a reactive diluent having a boiling point greater than 100 ℃ and containing a reactive functional group that reacts with the reactive functional group on the polymer at a temperature below the boiling point of the reactive diluent; wherein the coating composition has a solids content of at least 95% as measured according to test method ASTM D2369.

The invention may also be used in a method of providing sound and vibration damping through a substrate comprising: applying to a substrate a coating composition comprising: a mixture and a filler material, said comprising, or in some cases consisting of, or in some cases consisting essentially of: (a) a polymer prepared from one or more functional monomers comprising (meth) acrylic monomers, allyl monomers, or combinations thereof, each having an ethylenically unsaturated double bond and an additional reactive functional group, wherein at least some of the additional reactive functional groups of the functional monomers remain unreacted during formation of the polymer; and (b) a reactive diluent having a boiling point greater than 100 ℃ and containing a reactive functional group that reacts with the reactive functional group on the polymer at a temperature below the boiling point of the reactive diluent; wherein the coating composition has a solids content of at least 95% as measured according to test method ASTM D2369.

The invention can also be a substrate having a cured coating with a dry film thickness of at least 1 mm. The cured coating can be formed from a coating composition comprising: a mixture comprising, or in some cases consisting of, or in some cases consisting essentially of: (a) a polymer prepared from one or more functional monomers comprising (meth) acrylic monomers, allyl monomers, or combinations thereof, each having an ethylenically unsaturated double bond and an additional reactive functional group, wherein at least some of the additional reactive functional groups of the functional monomers remain unreacted during formation of the polymer; and (b) a reactive diluent having a boiling point greater than 100 ℃ and containing a reactive functional group that reacts with the reactive functional group on the polymer at a temperature below the boiling point of the reactive diluent; wherein the coating composition has a solids content of at least 95% as measured according to test method ASTM D2369.

The coating compositions described above can be applied alone or as part of a coating system, which can be deposited on many different substrates in many different ways. The coating system may comprise a number of identical or different coatings. The coating layer is typically formed when the coating composition deposited onto the substrate is at least partially cured by methods known to those skilled in the art (e.g., by exposure to heat). It should be noted that the above-described coating composition may be used for one or more of the coatings described in the following paragraphs.

The coating composition may be applied to the surface of the substrate in any of a number of different ways, non-limiting examples of which include spraying, dipping or dipping, extrusion coating, flow coating, brushing, rolling, and/or knife/blade coating.

Useful substrates include those formed from metallic substrates, polymeric substrates (e.g., formed from thermoset and/or thermoplastic materials), and combinations thereof. Suitable metal substrates that may be coated include ferrous metals such as iron, steel and alloys thereof, non-ferrous metals such as aluminum, zinc, magnesium and alloys thereof and combinations thereof. The substrate may be formed of cold rolled steel, electrogalvanized steel, such as hot-dipped electrogalvanized or electrogalvanized iron-zinc steel, aluminum or magnesium. The metal substrate to be treated may be bare, pretreated or precoated (e.g., by electrocoating) prior to application of the coating composition.

Non-limiting examples of useful thermoset materials include polyester, epoxy, phenolic, urea-formaldehyde, melamine, polyimide, polyisocyanurate, polyurethane and/or vulcanized rubber (e.g., reaction injection molded polyurethane) thermoset materials and combinations thereof.

Non-limiting examples of useful thermoplastic materials include polyesters, acrylic polymers, polyolefins (e.g., polyethylene and polypropylene), polyamides (e.g., nylon), polybenzimidazoles, vinyl polymers (e.g., polyvinyl chloride), polystyrene, fluoropolymers, polytetrafluoroethylene), polycarbonates, acrylonitrile-butadiene-styrene (ABS) copolymers, EPDM rubber, and/or polyurethane thermoplastic materials and combinations thereof.

According to the present invention, the coating composition may be applied to the substrate in a wet film thickness of from 1mm to 7mm, depending on the desired sound and vibration damping requirements or properties of the cured coating. Thicker membranes generally produce higher sound and vibration damping performance.

After application to the substrate, the coating composition may be subjected to a baking and/or curing step, such as 110 ℃ to 220 ℃, 140 ℃ to 210 ℃, 150 ℃ to 200 ℃, 175 ℃ to 190 ℃, and for any desired time (e.g., 5 minutes to 1 hour) sufficient to at least partially dry and/or cure the coating composition on the substrate. Optionally, according to the present invention, baking and/or curing may be performed at a temperature below the boiling point of the reactive diluent.

One or more additional baking and/or curing steps may be performed to suit a particular paint system configuration.

The dry film thickness of the coating can be increased from 0% to 100% from the applied wet film thickness depending on a variety of factors including, but not limited to, the drying rate and the amount of heat applied to the coating composition.

After the coating composition is applied to a substrate, either alone or in combination with one or more additional coating layers, and at least partially cured, the coating layer can exhibit a Composite Damping Loss Factor (CDLF) of 0.05 to 0.25, as measured according to Oberst ASTM E756-05 at temperatures of 10 ℃ to 30 ℃ and at frequencies of 198Hz to 202 Hz.

After the coating composition is applied to a substrate, alone or in combination with one or more additional coating layers, and at least partially cured, the coating layer can exhibit a water absorption of less than 15%, e.g., less than 10%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1%, according to such a test method, which measures a change (e.g., increase) in the weight of the coating layer based on the percent water absorption calculated by: the difference between the coating weight before exposure to water and the coating weight after exposure to water was divided by the coating weight before exposure to water and then multiplied by 100, as described in more detail in the examples below.

Aspects of the invention

1. A coating composition comprising:

a mixture, the mixture comprising:

(a) a polymer prepared from one or more functional monomers comprising (meth) acrylic monomers, allyl monomers, or combinations thereof, each having an ethylenically unsaturated double bond and an additional reactive functional group, wherein at least some of the additional reactive functional groups of the functional monomers remain unreacted during formation of the polymer; and

(b) a reactive diluent having a boiling point greater than 100 ℃ and containing a reactive functional group that reacts with a reactive functional group on the polymer at a temperature below the boiling point of the reactive diluent; and

a filler material, wherein the filler material is selected from the group consisting of,

wherein the coating composition has a solids content of at least 95% as measured according to test method ASTM D2369.

2. The coating composition according to aspect 1, wherein the functional monomer is selected from the group consisting of (meth) acrylate monomers, allyl monomers, and combinations thereof.

3. The coating composition according to aspect 2, wherein the functional monomer is selected from the group consisting of (meth) acrylate monomers, allyl glycidyl ether, and combinations thereof.

4. The coating composition according to aspect 2, wherein the functional monomer is selected from (meth) acrylate monomers.

5. The coating composition according to any of aspects 1-4, wherein the reactive functional group of the functional monomer comprises an epoxy group, a hydroxyl group, an anhydride group, an amino group, an acid functional group (such as a carboxylic acid group or a sulfonic acid group), or a combination thereof.

6. The coating composition of aspect 5, wherein the reactive functional group of the functional monomer comprises an epoxy group.

The coating composition according to aspect 6, wherein the functional monomer comprises glycidyl (meth) acrylate.

8. The coating composition according to any one of aspects 1 to 7, wherein the polymer (a) is a copolymer.

9. The coating composition according to claim 8, wherein the polymer is a copolymer prepared from at least one functional monomer and monomers comprising at least ethylenic unsaturation but no additional reactive functional groups.

10. The coating composition according to aspect 8 or 9, wherein the polymer (a) is a copolymer prepared from one or more functional monomers and one or more ethylenically unsaturated monomers that are free of epoxy groups, preferably free of hydroxyl groups, anhydride groups, amino groups and acid functional groups, such as carboxylic acid groups or sulfonic acid groups.

11. The coating composition according to any one of aspects 8 to 10, wherein the polymer (a) comprises 1 to 90 wt. -%, such as 5 to 70 wt. -%, or 30 to 50 wt. -% or 20 to 40 wt. -% of the functional monomer, based on the total weight of the polymer.

12. The coating composition according to aspect 10 or claim 11 referring back to aspect 10, wherein the ethylenically unsaturated monomer free of epoxide groups is selected from vinyl aromatic monomers such as styrene and vinyl toluene; (meth) acrylates, such as alkyl (meth) acrylates, preferably containing 1 to 20 atoms in the alkyl group; (meth) acrylonitrile; (ii) acrylamide; vinyl halides such as vinyl chloride; vinylidene halides such as vinylidene fluoride; vinyl esters such as vinyl acetate; a terpene; and combinations thereof.

13. The coating composition according to aspect 12, wherein the ethylenically unsaturated monomer free of epoxy groups is selected from vinyl aromatic monomers such as styrene and vinyl toluene; alkyl esters of (meth) acrylic acid, preferably containing 1 to 20 atoms in the alkyl group; and combinations thereof.

14. The coating composition according to aspect 13, wherein the polymer (a) comprises 40 to 95 wt. -%, such as 50 to 80 wt. -%, based on the total weight of the polymer (a), of the one or more alkyl esters of (meth) acrylic acid.

15. The coating composition according to any of aspects 1-14, wherein the weight average molecular weight of the polymer (a) is 1,000g/mol to 100,000g/mol, such as 1,000g/mol to 3,000g/mol or 3,000g/mol to 5,000g/mol or 5,000g/mol to 9,000g/mol or 9,000g/mol to 30,000g/mol, as determined by gel permeation chromatography using polystyrene standards in Tetrahydrofuran (THF).

16. The coating composition according to any one of aspects 1-14, wherein the weight average molecular weight of the polymer (a) is at least 150,000g/mol, as determined by gel permeation chromatography using polystyrene standards in Tetrahydrofuran (THF).

17. The coating composition according to any one of aspects 1-16, wherein the polymer (a) is substantially free of acid functional groups.

18. The coating composition according to any one of aspects 1-17, wherein the reactive diluent (b) is selected from the group consisting of polymeric compounds, non-polymeric compounds, and combinations thereof.

19. The coating composition according to any one of aspects 1-18, wherein the reactive functional group of the reactive diluent (b) comprises an epoxy group.

20. The coating composition according to aspect 19, wherein the reactive diluent (b) has an epoxy equivalent weight of from 50g/mol to 500g/mol, such as from 50g/mol to 200g/mol or from 200g/mol to 300g/mol, according to ASTM D1652.

21. The coating composition according to any one of aspects 1 to 20, wherein the reactive diluent (b) is a monofunctional reactive diluent.

22. The coating composition according to any of aspects 1 to 21, wherein the reactive diluent (b) is a glycidyl ester, such as branched C₉-C₁₁Glycidyl esters of carboxylic acids, preferably of neodecanoic acid.

23. The coating composition according to any of aspects 1-22, wherein the reactive diluent (a) is present in an amount of 5-70 wt. -%, such as 10-60 wt. -%, or 20-50 wt. -%, or 40-50 wt. -%, or 30-40 wt. -%, or 20-30 wt. -% or 10-20 wt. -%, based on the total weight of the mixture of the polymer (a) and the reactive diluent (b).

24. The coating composition according to any of aspects 1-23, wherein the polymer (a) is present in an amount of 30-95 wt. -%, such as 40-90 wt. -% or 50-80 wt. -% or 50-60 wt. -% or 60-70 wt. -% or 70-80 wt. -% or 80-90 wt. -%, based on the total weight of the mixture of the polymer (a) and the reactive diluent (b).

25. The coating composition according to any one of aspects 1-24, wherein the polymer (a) and the reactive diluent (b) are present as a single phase.

26. The coating composition according to any one of aspects 1-24, wherein the polymer (a) is dispersed in the reactive diluent (b).

27. The coating composition according to any one of aspects 1-26, wherein the mixture further comprises a second polymer dispersed in the reactive diluent.

28. The coating composition according to any of aspects 1-27, wherein the mixture of polymer (a) and reactive diluent (b) has a brookfield viscosity of 1,000 cps to 25,000 cps measured at 100rpm with a #6 spindle at a temperature of 25 ℃, in the absence of filler.

29. The coating composition according to any one of aspects 1-28, further comprising a catalyst capable of catalyzing the reaction between the polymer (a) and the reactive diluent (b).

30. The coating composition according to any of aspects 1-29, further comprising an antioxidant, a plasticizer, or a combination thereof.

31. The coating composition according to any one of aspects 1-30, wherein the composition is free of solvent or comprises a solvent amount of less than 5 wt.%, based on the total weight of the composition.

32. The coating composition according to any of aspects 1-31, wherein the filler material is an organic filler material, an inorganic filler material, or a combination thereof.

33. The coating composition according to any of aspects 1-32, wherein the filler material is present in the coating composition in an amount of 20-80 wt.%, such as 30-70 wt.% or 40-60 wt.%, based on the total weight of the coating composition.

34. The coating composition according to any of aspects 1-33, wherein the polymer (a) and reactive diluent (b) are present in the mixture in an amount of 20-100 wt. -%, such as 30-75 wt. -%, or 40-70 wt. -% or 50-60 wt. -%, based on the total weight of the mixture comprising the polymer (a) and reactive diluent (b), in total.

35. A coating applied to a substrate comprising a reaction product prepared from the coating composition according to any of aspects 1-34, which after curing has a dry film thickness of at least 1 mm.

36. The coating applied to a substrate according to aspect 35, which after curing exhibits a composite damping loss factor of 0.05 to 0.25, measured according to Oberst ASTM E756-05 at a temperature of 10 ℃ to 30 ℃ and at a frequency of 198Hz to 202 Hz.

37. The coating applied to a substrate according to aspect 35 or 36, which exhibits a water absorption of less than 15% after curing.

38. A method for providing sound and vibration damping through a substrate, comprising:

applying a coating to a substrate a composition according to any of aspects 1-34; and

at least partially curing the coating composition.

The following specific examples are provided for illustrative purposes only and are not intended to be limiting unless otherwise specified.

Examples

The preparation of examples of coating compositions is described below. The various materials listed below are in grams (g) or parts by weight unless otherwise indicated.

Example 1

Polyester intermediate 1 for seed stage stabilizer was prepared as follows:

TABLE 1

Charge #1 was charged to a 5-liter four-necked flask equipped with a motor-driven steel stirring blade, thermocouple, nitrogen inlet and water-cooled condenser. The reaction mixture was heated to reflux (initial reflux temperature about 130 ℃ C. and increased to about 155 ℃ C. at the end of the process). After the reaction mixture was melted, charge #2 was added to the reaction flask. After collecting 90% of the reaction (about 100 g), a sample was taken and the acid number was determined by titration. The reaction mixture was cooled to 130 ℃ when the acid number of the reaction mixture was 29-30. The reaction mixture was then air sparged and charge #3 was added to the reaction flask. The reaction mixture was maintained at 130 ℃ until the acid number was below 0.4. The acid value of the intermediate solution thus obtained was 0.4mg KOH/g resin (determined by titration); a weight average molecular weight (Mw) of 5,973g/mol and a number average molecular weight (Mn) of 3,595g/mol (as determined by gel permeation chromatography using polystyrene standards); and a free monomer glycidyl methacrylate content of 2.63 wt.% (determined by gel permeation chromatography).

Example 2

Stabilizer 1 was prepared as follows:

TABLE 2

¹VAZO 64 is 2, 2' -azobis (2-methylpropanenitrile), available from DuPont.

Charge #1 was added to a 5 liter four-necked flask and heated to 99 ℃ under a nitrogen blanket. Feeds #2 and #3 were added to the reaction flask over 3 hours at 99 ℃. After addition of feeds #2 and #3 was complete, feed #4 was used for rinsing. The reaction mixture was then maintained at 99 ℃ for 4 hours. When the hold was over, charge #5 was added and the reaction mixture was then heated to 135 ℃. The reaction mixture was kept at 135 ℃ for 4 hours. The acid value of the thus obtained seed stage stabilizer was 0.14mg KOH per g resin (determined by titration); a weight average molecular weight (Mw) of 18,434g/mol and a number average molecular weight (Mn) of 2,616g/mol (as determined by gel permeation chromatography using polystyrene standards); and a free methyl methacrylate monomer content of 1.47 wt.% and a free glycidyl methacrylate content of 0.13 wt.% (determined by gel permeation chromatography).

Example 3

Non-aqueous dispersion 1 was prepared as follows:

TABLE 3

¹VAZO 67 is 1, 1' -azobis (cyclohexanecarbonitrile), available from DuPont.

Charge #1 was charged to a 2 liter 4-neck flask equipped with a motor driven steel stir blade, thermocouple, nitrogen inlet, and water cooled condenser. The reaction mixture was heated to 90 ℃ by a temperature feedback control device through a thermocouple controlled nest. Feeds #2 and #3 were added over 10 minutes through an addition funnel and the reaction mixture was then held at 90 ℃ for 30 minutes. After hold, feeds #4 and #5 were added over 3 hours, and then the reaction mixture was held at 90 ℃ for 1 hour. After hold, charge #6 was added over 10 minutes, and then the reaction mixture was held at 90 ℃ for 1 hour. The volume average particle diameter of the thus obtained non-aqueous dispersion was 218nm (measured by Zetasizer).

Example 4

Non-aqueous dispersion 2 was prepared as follows:

TABLE 4

¹CARDURA E10 is VERSATIC^TMAcid 10 (a synthetic highly branched C)₁₀Isomeric saturated monocarboxylic acids) available from Momentive specialty Chemicals, Inc.

Charge #1 was charged to a 1-liter four-necked flask equipped with a motor-driven steel stirring blade, thermocouple, nitrogen inlet, and water-cooled condenser. The reaction mixture was heated to 50 ℃ and then the solvent in non-aqueous dispersion 1 (example 3) was evacuated at 28 inches Hg pressure. The resultant non-aqueous dispersion 2 had a Brookfield viscosity of 376 centipoise as measured at ambient/room temperature (25 ℃) using a #2 spindle at 50 rpm.

Example 5

Non-aqueous dispersion 3 was prepared as follows:

TABLE 5

Charge #1 was charged to a 1-liter four-necked flask equipped with a motor-driven steel stirring blade, thermocouple, nitrogen inlet, and water-cooled condenser. The reaction mixture was heated to 50 ℃ and then the solvent in non-aqueous dispersion 1 (example 3) was evacuated at 28 inches Hg pressure. The resultant non-aqueous dispersion 3 had a Brookfield viscosity of 2,527 cps measured at ambient/room temperature (25 ℃) using a #2 spindle at 100 rpm.

Example 6

Continuous acrylic copolymer 1 was prepared as follows:

TABLE 6

The continuous reactor set-up comprised a 300mL reactor and a 4L flash tank set-up. A300 mL reactor was initially filled with butyl cellosolve and heated to 210 ℃. At 210 ℃, the pumping of feed #1 was started and the residence time in the reactor was 5 minutes and the reactor pressure was maintained at 400-. The flash tank was heated to 170 ℃ and feed #2 was fed to the flash tank at 1.12 mL/min. The weight average molecular weight (Mw) of the resulting copolymer was 3,494g/mol (as measured by gel permeation chromatography using polystyrene standards); and ethylhexyl acrylate with a free monomer content of 0.32 wt.%, styrene of 0.04 wt.%, methyl methacrylate of 0.22 wt.% (determined by gel permeation chromatography), and glycidyl methacrylate of 0.40 wt.% (determined by high performance liquid chromatography).

Example 7

Resin a was prepared as follows:

70 parts of continuous acrylic copolymer 1 from example 6 and 30 parts of CARDURA E10 were charged into a beaker and placed in an oven at 110 ℃ for 2 hours and then mixed thoroughly with mechanical stirring.

Resin A had a Brookfield viscosity of 1,610 cps measured at a temperature of 27 ℃ using a #6 spindle at 100 rpm.

Example 8

Resin B was prepared as follows:

60 parts by weight of the non-aqueous dispersion 3 from example 5, 100 parts by weight of the continuous acrylic copolymer 1 from example 6 and 26 parts by weight of CARDURA E10 were charged into a beaker, placed in an oven at 110 ℃ for 2 hours and then thoroughly mixed with mechanical stirring.

Resin B had a Brookfield viscosity of 2,400 cps, measured at ambient/room temperature (25 ℃) using a #6 spindle at 100 rpm.

Coating composition

Preparation of

The ingredients listed in table 7 below were mixed in a vessel using an air driven motor with low agitation. The ingredients were added to the vessel in the order shown in table 7 and the mixing speed was increased to maintain a vortex throughout the addition.

TABLE 7

¹Resin A of example 7

²Non-aqueous Dispersion 3 of example 5

³Resin B of example 8

⁴Reaction product of propylene carbonate with JEFF Amine 400, prepared as in example A of US 7,288,595

⁵Carbon Black powder available from Columbian Chemicals

⁶Calcium oxide, available from Mississippi Lime Company

⁷Cyanoguanidine, obtainable from Alz Chem

⁸Dimethyl-1, 1,3- (3, 4-dichlorophenyl), available from Alz Chem

⁹Epoxy accelerators available from Ajinomoto Fine Techno Company

¹⁰Epoxy accelerators available from Ajinomoto Fine Techno Company

¹¹Calcium magnesium carbonate available from Specialty Minerals

Coating layer

Composite damping loss factor

The vibration damping of each coating was measured using Oberst ASTM test method E756-05 ("method for measuring vibration damping Properties of materials"), sections 3 and 10. The primary measure of acoustic damping in this test is the loss factor, the ratio of the loss modulus to the storage modulus of the material. The Oberst value typically ranges from 0.001 (which would be heard "on the fly") to 0.01 ("pound") to 0.1 ("bang") to 0.5 ("bang") for uncoated steel (1 mm thickness) with the coating effect increasing progressively.

The Oberst test is used to measure the sound loss factor of the coating-substrate composite. Each test sample was applied to an Oberst bar, which was a metal bar formed from a special oil hardened flat blank, AISI/SAE GRD 0-1, 1mm thick, 10mm wide and 240mm long, from McMaster-Carr, and cured as described above. The weight of each cured coating was 6.72+ -.0.05 grams over a 210mm coating length. The Oberst loss factor value was normalized to 6.72 grams (3.2 kg/m)²) A comparison is made. The composite damping loss factor is measured over a temperature range of-10 to 40 ℃ and at a frequency of 200 Hz.

TABLE 8

Water resistance

The coating was conditioned (draw down) on a 4 inch by 4.5 inch galvanized steel plate. The panels were weighed and recorded, and a 3 inch wide, 3 mm thick template was used to adjust the coating to a 4 inch length in the center of the panel. The coated panels were baked in an oven on the following schedule: 23 minutes at 155 ℃, then 18 minutes at 150 ℃ and then 30 minutes at 140 ℃. The panels were held at ambient temperature for 10 minutes between each bake. The baked panels were stored at room temperature for 24 hours prior to testing.

The baked plates were weighed and recorded before the test began. The difference between the weight of the panel without coating and the weight of the panel with the baked coating was calculated and recorded as the baked coating weight. The test panels were then placed in a 100% condensing humidity cabinet maintained at 40 ℃. After 7 days the plates were removed from the cabinet. After removal of the plate, the surface water was dried with paper towels and the plate was weighed immediately.

The percent water absorption was calculated by dividing the difference between the weight of the panel with baked coating before exposure to water and the weight of the panel with baked coating after exposure to water by the weight of the panel with baked coating before exposure to water, then multiplying by 100.

TABLE 9

¹In a 100% condensing humidity cabinet at 40 deg.C for 7 days

Those skilled in the art will appreciate that many modifications and variations are possible in light of the above disclosure without departing from the broad inventive concept described and illustrated herein. It should be understood, therefore, that the foregoing disclosure is merely illustrative of various exemplary aspects of the application and that numerous modifications and changes in light thereof will be suggested to those skilled in the art and are to be included within the spirit and purview of this application and the scope of the appended claims.

Claims

1. A coating composition comprising:

a mixture, the mixture comprising:

(a) a polymer prepared from one or more functional monomers comprising (meth) acrylic monomers, allyl monomers, or combinations thereof, each having an ethylenically unsaturated double bond and an additional reactive functional group; wherein at least some of the additional reactive functional groups of the functional monomer remain unreacted during the formation of the polymer; and

(b) a reactive diluent present in an amount of at least 10 weight percent based on the total weight of the polymer and reactive diluent, having a boiling point greater than 100 ℃ and a reactive functional group comprising an epoxy functional group, the reactive functional group on the reactive diluent reacting with the reactive functional group on the polymer at a temperature below the boiling point of the reactive diluent; and

2. The coating composition of claim 1, wherein the functional monomer comprises glycidyl (meth) acrylate.

3. The coating composition of claim 1, wherein the polymer comprises 1 to 70 weight percent of the functional monomer, based on the total weight of the polymer.

4. The coating composition of claim 1, wherein the polymer is a copolymer prepared from at least one functional monomer and at least one monomer comprising ethylenic unsaturation but not an additional reactive functional group.

5. The coating composition of claim 1, wherein the polymer has a weight average molecular weight of 1,000g/mol to 100,000g/mol as determined by gel permeation chromatography using polystyrene standards in tetrahydrofuran.

6. The coating composition of claim 1, wherein the polymer has a weight average molecular weight of at least 150,000g/mol as determined by gel permeation chromatography using polystyrene standards in tetrahydrofuran.

7. The coating composition of claim 1, wherein the polymer contains less than 1 wt.% acid functional groups based on the total weight of the polymer.

8. The coating composition of claim 1, wherein the reactive diluent is a monofunctional reactive diluent.

9. The coating composition of claim 1, wherein the reactive diluent is a multifunctional reactive diluent.

10. The coating composition of claim 1, wherein the reactive diluent is present in an amount of 10 to 70 weight percent based on the total weight of the mixture of the polymer and reactive diluent.

11. The coating composition of claim 1, wherein the polymer and the reactive diluent are present as a single phase.

12. The coating composition of claim 1, wherein the polymer is dispersed in the reactive diluent.

13. The coating composition of claim 12, wherein the mixture further comprises a second polymer dispersed in the reactive diluent.

14. The coating composition of claim 1, wherein a mixture comprising the polymer and the reactive diluent, in the absence of filler or any other component, has a Brookfield viscosity of 1,000 centipoise to 25,000 centipoise measured at 100rpm with a #6 spindle at ambient temperature.

15. The coating composition of claim 1, further comprising a catalyst capable of catalyzing a reaction between the polymer and the reactive diluent.

16. The coating composition of claim 1, further comprising an antioxidant, a plasticizer, or a combination thereof.

17. The coating composition of claim 1, wherein the composition is substantially free of solvent.

18. A coating applied to a substrate comprising a reaction product prepared from the coating composition of claim 1, the coating having a dry film thickness of at least 1mm after curing.

19. A coating applied to a substrate according to claim 18 having a composite damping loss factor of from 0.05 to 0.25 measured according to Oberst ASTM E756-05 at a temperature of from 10 ℃ to 30 ℃ and at a frequency of from 198Hz to 202 Hz.

20. The coating applied to a substrate according to claim 18, which exhibits a water absorption of less than 15% after curing.

21. A method for providing sound and vibration damping through a substrate, comprising:

applying to a substrate a coating composition according to claim 1; and

at least partially curing the coating composition.